Solid composition consisting of heterocyclic compounds and/ or oxime esters and inert porous carrier materials and the use thereof as stable bleach activator component in detergents, bleaches and cleaners

ABSTRACT

The invention concerns a solid composition substantially comprising between 5 and 98 parts by weight of heterocyclic compounds (I) R 1 —X—L 1 , wherein L 1  stands for groups with a cyclic carbamate, a lactoneoxy or a lactam structure, X means a carbonyl, a double carbonyl or a heterocarbonyl group, and R 1  designates an organic group or a second L 1  group, and/or oxime esters (II), wherein L 2  stands for an oxime group (a) or (b), R 2 , R 3  and Z 4  designating organic groups or bridge members, L 3  stands for the R 1  group, a second L 2  oxime group or a carbon ester group, carbon amide group, phenolate group, vinyloxy group, sulphoneamide group, imidazole group, amidolactam group, cyclic carbamate group, lactoneoxy group or lactam group, and m means 0 or 1. The composition further comprises between 2 and 95 parts by weight of inert porous carrier materials with an internal area of between 10 and 500 m 2 /g. The solid composition described is suitable as a stable bleach-activator component in washing, bleaching and cleaning agents.

[0001] Solid composition consisting of heterocyclic compounds and/oroxime esters and inert porous carrier materials and the use thereof asstable bleach activator component in detergents, bleaches and cleaners

[0002] The present invention relates to a solid composition consistingof heterocyclic compounds with cyclic carbamate, lactonoxy or lactamstructure and/or oxime esters and inert porous carrier materials whoseinternal surface area has a particular value. The invention furthermorerelates to a process for preparing this solid composition and to its usein detergents, bleaches and cleaners, especially as stable bleachactivator component.

[0003] A number of cold bleach activators, including some of thecompounds I and II defined hereinafter, are liquid or plastic in thepure form and, accordingly, can be converted only with great difficultyinto free-flowing granules or powders using conventional auxiliaries andformulation methods. Free-flowing formulations with no tendency toagglomerate are, however, required for use in detergent and some cleanerformulations.

[0004] Conventional drying processes for producing solids fromsolutions, such as spray drying, frequently give unsatisfactory resultsfor cold bleach activators which are solid in pure form, because thesesubstances are, as a rule, very hygroscopic and mostly have relativelylow melting points. The applicability of crystallization processes isjust as low because these substances are often prone to formsupersaturated solutions, i.e. crystallization is greatly inhibited andthus uncontrollable.

[0005] It is an object of the present invention to provide astorage-stable solid, free-flowing form for cold bleach activators witha heterocyclic structure, in particular using auxiliaries which aredescribed in large numbers in the prior art for such purposes. It wasmoreover intended that these compositions also be improved in theirformulated form with regard to the dissolving rate and the activity inthe wash liquor.

[0006] Thus, for example, DE-A 27 33 849 (1) discloses solid cold bleachactivator formulations for detergents and cleaners, the only cold bleachactivators mentioned are acyl compounds such as diacetyl-methylamine ordiacetylbutylamine. These cold bleach activators are mixed withadsorbents such as kieselguhr, silicates, silicas or aluminum oxide.However, (1) contains no information on the internal surface area andaverage particle size of these adsorbents.

[0007] DE-A 34 44 960 (2) relates to a coarse-particle adsorbent forliquid and pasty detergent and cleaner formulations which may, interalia, contain bleach activators. The granules of adsorbent and detergentor cleaner formulation produced in this way can also be dusted orsurface-coated with fine-particle powders. Examples of such dustingpowders are zeolites or silica aerogel with a particle size of from0.001 to 0.1 mm, but no information is given on their internal surfacearea.

[0008] EP-A 170 386 (3) discloses bleach systems which contain asbleaching agent inter alia N-acyl- or N-benzoyl-6-aminoperoxy-caproicacid. These bleach systems are employed in detergent formulations whichcontain sodium aluminum silicates, eg. zeolite A, as builder which ispresent separate from the bleach system.

[0009] EP-A 382 464 (4) discloses a coating or encapsulation process forsolid particles or liquid drops, for example bleaches, with polyethyleneglycols, polyethylene oxides, polyvinylpyrrolidone, oxidizedpolyethylene or similar substances. In this case, fine-particlesubstances such as Aerosil® 380 or Aerosil R 972 are added asformulation aids (“crumbling agents”).

[0010] We have now found a solid composition consisting essentially of5-98 parts by weight of heterocyclic compounds of the general formula I

R¹—X—L¹   (I)

[0011] where

[0012] L¹ is (a) a cyclic carbamate residue of the formula

[0013] (b) a lactonoxy residue of the formula

[0014] or

[0015] (c) a lactam residue of the formula

[0016] where

[0017] Z¹ to Z³ are 1,2-, 1,3-, 1,4- or 1,5-alkylene groups which have 2to 20 carbon atoms, and which can additionally be functionalized by oneto three hydroxyl groups, C₁-C₄-alkoxy groups, amino groups,C₁-C₄-alkylamino groups, di-C₁-C₄-alkylamino groups, chlorine atoms,bromine atoms, nitro groups, cyano groups, carboxyl groups, sulfogroups, carboxy-C₁-C₄-alkyl groups, carboxamide groups or phenyl, tolylor benzyl radicals, it likewise being possible for aromatic nuclei inturn to be substituted by said radicals, or interrupted by one or twonon-adjacent oxygen atoms, amino groups, C₁-C₄-alkylamino groups orcarbonyl groups, and

[0018] T is hydrogen or C₁-C₄-alkyl,

[0019] X is an oxygen-containing group of the formula

[0020] where

[0021] Y is hydrogen, ammonium which can be unsubstituted or substitutedby organic radicals, or C₁-C₄-alkyl, and

[0022] A is a chemical bond or a C₁-C₁₈-alkylene group, aC₂-C₁₈-alkenylene group, a C₅-C₃₂-cycloalkylene group, aC₇-C₃₀-aralkylene group, a C₆-C₁₈-arylene group or a C₃-C₁₈-hetarylenegroup, it additionally being possible for aliphatic structural units tobe functionalized by one to five hydroxyl groups, C₁-C₄-alkoxy groups,amino groups, C₁-C₄-alkylamino groups, di-C₁-C₄-alkylamino groups,chlorine atoms, bromine atoms, nitro groups, cyano groups, carboxylgroups, sulfo groups, carboxy-C₁-C₄-alkyl groups, carboxamide groups orphenyl, tolyl or benzyl radicals, it likewise being possible foraromatic, cycloaliphatic and hetero-aromatic structural units to besubstituted by said radicals, or interrupted by one to eightnon-adjacent oxygen atoms, amino groups, C₁-C₄-alkylamino groups orcarbonyl groups, and

[0023] R¹ has the following meaning: C₁-C₃₀-alkyl, C₂-C₃₀-alkenyl,C₅-C₁₈-cycloalkyl, C₇-C₁₈-aralkyl, C₆-C₁₈-aryl or C₃-C₁₈-hetaryl, itbeing additionally possible for aliphatic radicals to be functionalizedby one to five hydroxyl groups, C₁-C₄-alkoxy groups, amino groups,C₁-C₄-alkylamino groups, di-C₁-C₄-alkylamino groups, chlorine atoms,bromine atoms, nitro groups, cyano groups, carboxyl groups, sulfogroups, carboxy-C₁-C₄-alkyl groups, carboxamide groups or phenyl, tolylor benzyl radicals, it likewise being possible for aromatic,cycloaliphatic and heteroaromatic structural units to be substituted bysaid radicals, or interrupted by one to eight non-adjacent oxygen atoms,amino groups, C₁-C₄-alkylamino groups or carbonyl groups, or aheterocyclic radical L¹,

[0024] and/or oxime esters of the general formula II

[0025] where

[0026] L² is an oxime moiety of the formula

[0027] where

[0028] R² and R³ are hydrogen, C₁-C₃₀-alkyl, C₂-C₃₀-alkenyl,C₅-C₁₈-cycloalkyl, C₇-C₁₈-aralkyl, C₆-C₁₈-aryl or C₃-C₁₈-hetaryl, itbeing additionally possible for aliphatic radicals to be functionalizedby one to five hydroxyl groups, C₁-C₄-alkoxy groups, amino groups,C₁-C₄-alkylamino groups, di-C₁-C₄-alkylamino groups, chlorine atoms,bromine atoms, nitro groups, cyano groups, carboxyl groups, sulfogroups, carboxy-C₁-C₄-alkyl groups, carboxamide groups or phenyl, tolylor benzyl radicals, it likewise being possible for aromatic,cycloaliphatic and heteroaromatic structural units to be substituted bysaid radicals, or interrupted by one to eight non-adjacent oxygen atoms,amino groups, C₁-C₄-alkylamino groups or carbonyl groups, and

[0029] Z⁴ is 1,3-, 1,4-, 1,5-, 1,6-, 1,7- or 1,8-alkylene groups whichhave 3 to 30 carbon atoms and which can additionally be functionalizedby one to five hydroxyl groups, C₁-C₄-alkylamino groups,di-C₁-C₄-alkylamino groups, chlorine atoms, bromine atoms, nitro groups,cyano groups, carboxyl groups, sulfo groups, carboxy-C₁-C₄-alkyl groups,carboxamide groups or phenyl, tolyl or benzyl radicals, it likewisebeing possible for aromatic nuclei in turn to be substituted by saidradicals, or interrupted by one or two non-adjacent oxygen atoms, aminogroups, C₁-C₄-alkylamino groups or carbonyl groups,

[0030] L³ is the radical R¹, a second oxime moiety L² or

[0031] (a) a carboxylic ester residue of the formula

[0032] (b) a carboxamide residue of the formula

[0033] (c) a phenolate residue of the formula

[0034] (d) a vinyloxy radical of the formula

—O—CR²═CHR³

[0035] (e) a sulfonamide residue of the formula

[0036] (f) an imidazole residue of the formula

[0037] (g) an amidolactam residue of the formula

[0038] (h) a cyclic carbamate residue of the formula

[0039] (j) a lactonoxy residue of the formula

[0040] or

[0041] (k) a lactam residue of the formula

[0042] where

[0043] R¹, R², R³, T, Z¹ to Z³ and A have the abovementioned meanings,

[0044] R⁴ is hydrogen, a carboxyl group, a sulfo group, a phosphonogroup or the alkali metal or ammonium salt thereof, and

[0045] m is the number 0 or 1

[0046] and 2-95 parts by weight of inert porous carrier materials withan internal surface area of from 10 to 500 m²/g.

[0047] The variables Z¹ bis Z³ in the heterocyclic systems (a) to (c)can be, in particular, C₂-C₁₀-alkylene groups of the followingstructure:

[0048] where, in the case of non-symmetrical alkylene groups, inprinciple both ways of incorporation into the rings are possible. Thevariables Z¹ to Z³ can be functionalized or interrupted as stated.

[0049] Typical examples of the linker A are the following:

[0050] as linear or branched C₁-C₁₈-alkylene group, in particularC₆-C₁₂-alkylene group, it is possible for methylene, 1,2-ethylene,1,1-ethylene, 1,3-propylene, 1,2-propylene, 1,1-propylene,2,2-propylene, 1,4-butylene, 1,2-butylene, 2,3-butylene, pentamethylene,3-methyl-1,5-pentylene, hexamethylene, heptamethylene, octamethylene,nonamethylene, decamethylene, undecamethylene, dodecamethylene,tetradeca-methylene, hexadecamethylene or octadecamethylene to occur;

[0051] as linear or branched C₂-C₁₈-alkenylene group, in particularC₆-C₁₂-alkenylene group, it is possible for linkers with one, two orthree olefinic double bonds to occur, eg. 1,2-ethenylene,1,3-propenylene, 1,4-but-2-enylene, 1,6-hex-3-enylene, 1,8-oct-4-enyleneor 1,12-dodec-6-enylene;

[0052] suitable as C₅-C₃₂-cycloalkylene groups, in particularC₅-C₁₀-cycloalkylene groups, are 1,2- or 1,3-cyclopentylene, 1,2-, 1,3-or 1,4-cyclohexylene, 1,2-, 1,3- or 1,4-cyclo-heptylene, 1,2-, 1,3-,1,4- or 1,5-cyclooctylene or groups of the formula

[0053] suitable as C₇-C₃₀-aralkylene groups, in particular unsubstitutedor alkyl-substituted C₇-C₂₂-phenylalkylene and -diphenyl-alkylenegroups, are groups of the formula

[0054] particularly suitable as C₆-C₁₈-arylene groups, in particularunsubstituted or alkyl-substituted phenylene, biphenylylene ornaphthylene groups, are 1,4-, 1,3- and 1,2-phenylene, but also groups ofthe formula

[0055] suitable as C₃-C₁₈-hetarylene groups, in particular five- orsix-membered C₃-C₁₂-hetarylene groups with one or two hetero-atoms fromthe group of nitrogen, oxygen and sulfur, are groups of the formula

[0056] examples of suitable structures interrupted by oxygen or aminogroups, in particular NH or N(CH₃) groups, are the following structures:

[0057] with n=2 to 8 and m=2 to 5.

[0058] Suitable meanings for the radical R¹ are the following:

[0059] suitable as C₁-C₃₀-alkyl group are, for example, methyl, ethyl,n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl,n-pentyl, iso-pentyl, sec-pentyl, tert-pentyl, neo-pentyl, n-hexyl,n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, iso-nonyl, n-decyl, n-undecyl,n-dodecyl, n-tridecyl, iso-tridecyl, n-tetradecyl, n-pentadecyl,n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl or n-eicosyl;C₆-C₁₈-alkyl groups are preferred, especially C₈-C₁₂-alkyl groups;

[0060] suitable as C₂-C₃₀-alkenyl group are, for example, vinyl, allyl,2-methyl-2-propenyl or the corresponding radical derived from oleicacid, linoleic acid or linolenic acid; C₁₆-C₂₂-alkenyl groups arepreferred;

[0061] particularly suitable as C₅-C₁₈-cycloalkyl group areC₅-C₁₀-cycloalkyl groups, eg. cyclopentyl, cyclohexyl, 2-, 3- or4-methylcyclohexyl, 2,3-, 2,4-, 2,5- or 2,6-dimethylcyclohexyl,cycloheptyl or cyclooctyl;

[0062] particularly suitable as C₇-C₁₈-aralkyl, in particularC₇-C₁₂-aralkyl, group are alkyl-substituted phenylalkyl groups, eg.benzyl, 2-, 3- or 4-methylbenzyl, 2-phenylethyl, 3-phenyl-propyl,4-phenylbutyl, 2-, 3- or 4-ethylbenzyl, 3- or 4-isopropylbenzyl or 3- or4-butylbenzyl;

[0063] suitable as C₆-C₁₈-aryl group are, for example, phenyl, 2-, 3-or4-biphenylyl, α- or β-naphthyl, 2-, 3- or 4-methylphenyl, 2-, 3- or4-ethylphenyl, 3- or 4-isopropylphenyl, 3- or 4-butylphenyl or 3- or4-(2-ethylhexyl)phenyl; C₆-C₁₄-aryl groups are preferred, especiallyphenyl and alkyl-substituted phenyl;

[0064] particularly suitable as C₃-C₁₈-hetaryl group are five- orsix-membered C₃-C₁₂-hetaryl groups with one or two heteroatoms from thegroup of nitrogen, oxygen and sulphur; examples thereof are:

[0065] examples of suitable aliphatic radicals interrupted by oxygen oramino groups, in particular NH or N(CH₃) groups, are the followingstructures:

[0066] with n=2 to 8 and m=2 to 5.

[0067] The variables Z¹ to Z³, A and R¹ defined above can additionallybe functionalized by the stated groups. In this connection C₁-C₄-alkoxygroups are in particular methoxy, ethoxy, n-propoxy, isopropoxy,n-butoxy, isobutoxy, sec-butoxy or tert-butoxy. Preferred amino groupsare —NH₂, —NH (CH₃), —NH (CH₂CH₃), —N(CH₃)₂ and —N(CH₂CH₃)₂. Examples ofcarboxy-C₁-C₄-alkyl groups are carboxymethyl, carboxyethyl,carboxypropyl, carboxybutyl or carboxy-tert-butyl.

[0068] The oxygen-containing group X in which one or two oxygen atomsare linked by a double bond on carbon, sulfur or phosphorus atoms, ie.are carbonyl or heterocarbonyl functionalities, is preferably

[0069] In the case where R¹=L¹, the two heterocyclic radicals L¹ bondedto the group X are preferably the same.

[0070] A particularly preferred solid composition is one in which theradical R¹ in the heterocyclic compounds I is C₆-C₁₈-alkyl,C₆-C₁₈-alkenyl, C₇-C₁₂-aralkyl, phenyl or alkyl-substituted phenyl witha total of up to 14 carbon atoms or a second heterocyclic radical L¹which has the same structure as the first heterocyclic radical L¹. Witha view to the preferred use of the heterocyclic compounds I as coldbleach activators in detergents, bleaches and cleaners, it has provenbeneficial for R¹ to be a long-chain or bulky radical with correspondinghydrophobicity.

[0071] The following types of structures of the heterocyclic compounds Iare preferably employed:

[0072] (1) N-Acyloxazolidones of the formula

[0073] (2) N-Acyl-1,3-tetrahydrooxazinones of the formula

[0074] (3) Acyloxy-γ-butyrolactone der Formel

[0075] (4) Acyloxy-γ-valerolactones of the formula

[0076] (5) O-Acylpantolactones of the formula

[0077] (6) Acyloxy-δ-valerolactones of the formula

[0078] (7) Acyloxy-ε-caprolactones of the formula

[0079] (8) Acyl-γ-butyrolactams of the formula

[0080] (9) N-Acyl-δ-valerolactams of the formula

[0081] (10)N-Acyl-ε-caprolactams of the formula

[0082] (11)N,N′-Carbonylbisoxazolidones of the formula

[0083] (12) N,N′-Carbonylbis-1,3-tetrahydrooxazinones of the formula

[0084] (13)Carbonic acid bis-γ-butyrolactones of the formula

[0085] (14) Carbonic acid bis-γ-valerolactones of the formula

[0086] (15) O,O′-Carbonylbispantolactones of the formula

[0087] (16)Carbonic acid bis-δ-valerolactones of the formula

[0088] (17)Carbonic acid bis-ε-caprolactones of the formula

[0089] (18)N,N′-Carbonylbis-γ-butyrolactams of the formula

[0090] (19)N,N′-Carbonylbis-δ-valerolactams of the formula

[0091] (20) N,N′-Carbonylbis-ε-caprolactams of the formula

[0092] (21)doubled N-acyloxazolidones of the formula

[0093] (22)doubled N-acyl-1,3-tetrahydrooxazinones of the formula

[0094] (23) doubled acyloxy-γ-butyrolactones of the formula

[0095] (24) doubled acyloxy-γ-valerolactones of the formula

[0096] (25) doubled O-acylpantolactones of the formula

[0097] (26) doubled acyloxy-δ-valerolactones of the formula

[0098] (27) doubled acyloxy-ε-caprolactones of the formula

[0099] (28)doubled acyl-γ-butyrolactams of the formula

[0100] (29) doubled acyl-δ-valerolactams of the formula

[0101] (30) doubled N-acyl-ε-caprolactams of the formula

[0102] The radical R¹ in types (1) to (10) of structure is, inparticular, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl,n-dodecyl, cyclohexyl, benzyl, phenyl or 2-, 3- or 4-methyl-phenyl.

[0103] The linker A in types (21) to (30) of structure is, inparticular, hexamethylene, octamethylene, decamethylene,dodeca-methylene, 1,3- or 1,4-cyclohexylene or 1,4-, 1,3- or1,2-phenylene; of particular interest for A is 1,4-phenylene (derivedfrom terephthalic acid).

[0104] The following meanings, besides hydrogen, are suitable for theradicals R² and R³ in the oxime esters II, which can be identical ordifferent:

[0105] examples of suitable linear or branched C₁-C₃₀-alkyl groups aremethyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl,tert-butyl, n-pentyl, iso-pentyl, sec-pentyl, tert-pentyl, neo-pentyl,n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl,n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl,n-octadecyl, n-nonadecyl or n-eicosyl; C₁-C₁₂-alkyl groups arepreferred, especially C₁-C₄-alkyl groups;

[0106] examples of suitable linear or branched C₂-C₃₀-alkenyl groups arevinyl, allyl, 2-methyl-2-propenyl or the corresponding radical derivedfrom oleic acid, linoleic acid or linolenic acid; C₂-C₆-alkenyl andC₁₆-C₂₂-alkenyl groups are preferred;

[0107] particularly suitable C₅-C₁₈-cycloalkyl groups areC₅-C₁₀-cycloalkyl groups, eg. cyclopentyl, cyclohexyl, 2-, 3- or4-methylcyclohexyl, 2,3-, 2,4-, 2,5- or 2,6-dimethylcyclohexyl,cycloheptyl or cyclooctyl;

[0108] particularly suitable C₇-C₁₈-aralkyl, especially C₇-C₁₂-aralkyl,groups are alkyl-substituted phenylalkyl groups, eg. benzyl, 2-, 3- or4-methylbenzyl, 2-phenylethyl, 3-phenylpropyl, 4-phenylbutyl, 2-, 3- or4-ethylbenzyl, 3- or 4-isopropylbenzyl or 3- or 4-butylbenzyl;

[0109] examples of suitable C₆-C₁₈-aryl groups are phenyl, 2-, 3- or4-biphenylyl, α- or β-naphthyl, 2-, 3- or 4-methylphenyl, 2-, 3- or4-ethylphenyl, 3- or 4-isopropylphenyl, 3- or 4-butyl-phenyl or 3- or4-(2-ethylhexyl)phenyl; C₆-C₁₄-aryl groups are preferred, especiallyphenyl and alkyl-substituted phenyl;

[0110] particularly suitable C₃-C₁₈-hetaryl groups are five- orsix-membered C₃-C₁₂-hetaryl groups with one or two heteroatoms from thegroup of nitrogen, oxygen and sulfur; examples thereof are:

[0111] examples of suitable aliphatic radicals interrupted by oxygen oramino groups, especially NH or N(CH₃) groups, are the followingstructures:

[0112] with p=2 to 8 and q=2 to 5.

[0113] The variable Z⁴ in the cyclic oxime moieties L² can mean, inparticular, C₃-C₁₂-alkylene groups of the following structure:

[0114] where the variable Z⁴ can be functionalized or interrupted asstated.

[0115] The variables Z¹ to Z³ in the heterocyclic systems (h), (j) and(k) can be, in particular, C₂-C₁₀-alkylene groups of the followingstructure:

[0116] where, in the case of non-symmetrical alkylene groups, inprinciple both ways of incorporation into the rings are possible. Thevariables Z¹ to Z³ can be functionalized or interrupted as stated.

[0117] Particularly suitable unsubstituted or substituted hydrocarbonradicals R¹ for the variable L³ in the oxime esters II are C₁-C₁₈-alkylradicals, C₂-C₁₈-alkenyl radicals, C₇-C₁₂-aralkyl radicals or phenyl oralkyl-substituted phenyl with a total of up to 14 carbon atoms. Typicalexamples thereof are:

[0118] methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl,n-octyl, n-nonyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl,n-octadecyl, benzyl, 2-phenylethyl, 4-phenylbutyl, phenyl and o-, m- orp-tolyl.

[0119] Particularly suitable carboxylic ester residues (a) for L³ are:

[0120] Particularly suitable carboxamide residues (b) for L³ are:

[0121] Particularly suitable phenolate residues (c) for L³ are:

[0122] and the relevant sodium or potassium salts.

[0123] Particularly suitable vinyloxy radicals (d) for L³ are:

[0124] Particularly suitable sulfonamide residues (e) for L³ are:

[0125] Particularly suitable imidazole residues (f) for L³ are:

[0126] Particularly suitable amidolactam residues (g) for L³ are:

[0127] Particularly suitable cyclic carbamate residues (h) for L³ are:

[0128] Particularly suitable lactonoxy residues (j) for L³ are:

[0129] T in the general formula for the lactonoxy residue (j) ispreferably hydrogen or methyl.

[0130] Particularly suitable lactam residues (k) for L³ are:

[0131] Typical examples of the linker A in the oxime esters II arelike-wise those stated above for the oxygen-containing group X in theheterocyclic compounds I.

[0132] The linker A in the oxime esters II is, in particular, a chemicalbond (formally derived from oxalic acid) or 1,2-ethylene (derived fromsuccinic acid), 1,4-butylene (derived from adipic acid), hexamethylene(derived from suberic acid), octamethylene (derived from sebacic acid),1,3- or 1,4-cyclohexylene or 1,2-, 1,3- or 1,4-phenylene (derived fromphthalic acid, isophthalic acid or terephthalic acid).

[0133] The variables R¹, R², R³, Z¹ to Z⁴ and A defined above mayadditionally be functionalized by the stated groups. In this connection,C₁-C₄-alkoxy groups are, in particular, methoxy, ethoxy, n-propoxy,isopropoxy, n-butoxy, isobutoxy, sec-butoxy or tert-butoxy. Preferredamino groups are —NH₂, —NH(CH₃), —NH(CH₂CH₃), —N(CH₃)₂ and —N(CH₂CH₃)₂.Examples of carboxy-C₁-C₄-alkyl groups are carboxymethyl, carboxyethyl,carboxypropyl, carboxybutyl or carboxy-tert-butyl.

[0134] In a preferred embodiment there is use of oxime esters II inwhich L² is an oxime moiety of the formula

[0135] where

[0136] R⁵ and R⁶ are hydrogen, C₁-C₄-alkyl, especially methyl or ethyl,phenyl or benzyl, and

[0137] Z⁵ is 1,4-butylene, 1,5-pentylene or 1,6-hexylene.

[0138] Aldoxime or ketoxime moieties of this type are derived fromconventional aldehydes or ketones, for example from formaldehyde,acetaldehyde, propionaldehyde, benzaldehyde, phenylacetaldehyde,acetone, ethyl methyl ketone, diethyl ketone, acetophenone,henylacetone, benzophenone, cyclopentanone, cyclohexanone orcycloheptanone.

[0139] Furthermore, preferred oxime esters II are those where L³ is asecond oxime moiety L²; particularly preferred in this connection arethose oxime esters II where L² and L³ are the same oxime moiety.

[0140] Of particular interest are bisoxime esters II derived from oxalicacid, succinic acid, adipic acid, phthalic acid, isophthalic acid orterephthalic acid and aliphatic ketones with 3 to 6 carbon atoms or fromC₅-C₇-cycloalkanones. Systems of this type can be prepared in a simplemanner, for example by reacting the corresponding dicarbonyl chloridesor bromides with appropriate aliphatic or cycloaliphatic ketoximes inthe presence of bases.

[0141] Also of particular interest as bisoxime esters II are furthermorebisiminocarbonates which are formally derived from carbonic acid andaliphatic ketones with 3 to 6 carbon atoms or from C₅-C₇-cycloalkanones.Systems of this type can be prepared in a simple manner for example byreacting phosgene with the appropriate aliphatic or cycloaliphaticketoximes in the presence of bases.

[0142] The oxime esters II described, methods for preparing them andtheir use as bleach activators in detergents, bleaches and cleaners areknown in principle, for example from JP-A 06/336 468 (5), WO-A 93/04037(6), the article by A. Jumar, P. Held and W. Schulze in Z. Chem. 7(1967), 344-345 (7) or German Patent Application 1 95 41 012.2 (8).According to (7), non-symmetrical bisoxime esters II and monooximeesters II can be prepared in the case where m=0 (carbonic acidderivatives) via the intermediate stage of the correspondingchloroformyloxime.

[0143] It is, of course, also possible to employ mixtures of thehetero-cyclic compounds I with the oxime esters II in the solidcompositions according to the invention.

[0144] A high internal surface area of the inert porous carriermaterials is crucially important for the required properties of theresulting solid composition. The internal surface area is preferably inthe range from 50 to 480 m²/g, in particular 100 to 460 m²/g, especially180 to 450 m²/g.

[0145] The average particle size of the inert porous carrier materialsis also important but it can vary within a wider range than the internalsurface area. The best results are obtained with an average particlesize of from 10 nm to 100 μm, in particular 20 nm to 50 μm, especially 1μm to 20 μm, but the average particle sizes can, depending on the natureof the carrier material and the application of the solid compositionaccording to the invention, also be smaller, for example down to 3 nm,or larger, for example up to 2 mm, especially up to 500 μm.

[0146] Inert porous carrier materials which can be used are in principleall conventional types of such chemically inert materials. However,particularly suitable are silica gels, silicas, aluminum oxides, kaolinsor aluminum silicates or mixtures thereof.

[0147] Silica gels are colloidal shaped or unshaped silicas with anelastic or a solid consistency and with a loose to compact porestructure and high adsorption capacity. Silica gel surfaces have acidicproperties. Silica gel is usually prepared from water glass by reactionwith mineral acids.

[0148] Silicas which can be employed are, besides the silicas preparedin a wet process, particularly advantageously the highly dispersepyrogenic SiO₂ types which are obtained thermally, ie. normally preparedby flash hydrolysis of SiCl₄ (eg. Aerosils® or Sipernats®). In aparticularly preferred embodiment of the present invention, silica withan average (agglomerate) particle size of from 100 nm to 30 μm, inparticular 1 μm to 20 μm, and an SiO₂ content of 95-100, preferably98-100, % by weight is used.

[0149] Aluminum oxides occur in nature as, for example, aluminas orcorundum. The aluminum oxide is in the a modification in these cases.Industrially, a-Al₂O₃ is obtained from bauxite by the Bayer process.“Active” aluminum oxides with a high specific surface area which areparticularly suitable as adsorbents are prepared by precipitationprocesses from aluminum salt solutions or by calcination from a-aluminumhydroxide.

[0150] Kaolins are hydrated aluminum silicates (clays) which occurnaturally in soil and which are also called china clays because of theirformer principal use. The main constituents are the triclinic kaoliniteand the monoclinic dickite and nacrite together with montmorillonite andaluminum silicates in gel form (allophanes).

[0151] Aluminum silicates are compounds with various proportions ofAl₂O₃ and SiO₂, which occur in nature as andalusite, disthene, mullite,sillimanite, etc. Aluminum silicate minerals in which Al occupies sitesin the crystal lattice in place of Si are the alumosilicates (eg.ultramarines, zeolites, feldspars).

[0152] Freshly precipitated aluminum silicates are finely dispersed andhave a large surface area and high adsorption capacity.

[0153] The ratio of heterocyclic compounds I or oxime esters II andinert porous carrier materials in the solid composition according to theinvention can vary within certain limits depending on the method forpreparing the solid composition and the material properties of thecomponents employed. A preferred ratio is 10-95 parts by weight of I orII to 5-90 parts by weight of carrier, in particular 30-90 parts byweight of I or II to 10-70 parts by weight of carrier. The stated partsby weight of I or II are always based on anhydrous or solvent-freecompound I or II. For economic reasons, it is desirable to maximize theproportion of heterocyclic compounds I or oxime esters II.

[0154] The solid composition according to the invention is, as a rule,homogeneously composed of the components employed. The hetero-cycliccompounds I and the oxime esters II and, where appropriate, otherauxiliaries are uniformly drawn into the interior of the carriermaterial particles and are uniformly distributed therein, because theyhave a relatively large internal surface area. There is normally nonoticeable gradient of concentration of the substances which are drawnin between the inner and outer surface of the particles or particleaggregates, so that it is not possible to speak of “coating”.

[0155] It may be advantageous for the properties of the solidcomposition according to the invention if it contains, in addition tothe stated parts by weight of I and II and carrier material, 0.5-70parts by weight, in particular 2-40 parts by weight, especially 5-25parts by weight, of anionic, nonionic or zwitterionic surfactants,carboxyl-containing polymers, polysaccharides, polyalkylene glycols,acidic alkali metal or alkaline earth metal salts of inorganic acids,neutral alkali metal salts, aliphatic C₈-C₁₈-monocarboxylic acids,aliphatic di-or tricarboxylic acids, aromatic mono- or dicarboxylicacids, it being possible for the abovementioned carboxylic acidsadditionally to contain hydroxyl and amino groups in the molecule,aliphatic C₃-C₇-monohydroxycarboxylic acids or mixtures thereof.

[0156] Examples of suitable anionic surfactants in this case are alkalimetal salts of fatty acids (soaps), alkylbenzenesulfonates,alkanesulfonates, α-olefinsulfonates, hydroxyalkanesulfonate, α-sulfofatty acid esters, alkyl sulfates, alkyl ether sulfates or fatty alcoholether sulfates. Of these, alkylbenzene-sulfonates, especially the alkalimetal and ammonium salts of linear C₁₁-C₁₃-alkylbenzenesulfonates, eg.sodium dodecylbenzenesulfonate, are preferred.

[0157] Examples of nonionic surfactants used in this case are alcoholalkoxylates, especially fatty alcohol alkoxylates, and alkylphenolalkoxylates, fatty acid alkylolamides and alkyl glycosides, especiallyC₈-C₁₆-monoalkyl glucosides. Of these, ethoxylates and propoxylates ofsaturated or unsaturated C₁₂-C₂₀ fatty alcohols, eg. coconut fatty andtallow fatty alcohol ethoxylates, are preferred.

[0158] Examples of suitable zwitterionic surfactants in this case aresecondary and tertiary amine oxides.

[0159] Suitable carboxyl-containing polymers are, in particular,homopolymers of acrylic acid and methacrylic acid, and copolymerscontaining acrylic acid and/or methacrylic acid, and the relevant alkalimetal or ammonium salts. Acrylic acid/maleic acid copolymers areparticularly preferred, especially in partially neutralized form, eg.acrylic acid/maleic acid copolymer which is about 50% in the form of thesodium salt (acrylic acid:maleic acid ratio=70:30 by weight).

[0160] The most advantageous polysaccharides are starch, amylose andderivatives of these naturally occurring polysaccharides such ascarboxymethylcellulose, cellulose acetate hydrogen phthalate,ethylcellulose or sulfated cellulose ethers. Of these, it is possible toemploy starch itself most favorably.

[0161] Particularly suitable polyalkylene glycols are polyethyleneglycols and ethylene oxide/propylene oxide copolymers.

[0162] Particularly suitable acidic alkali metal and alkaline earthmetal salts of inorganic acids are sodium bicarbonate and sodiumbisulfate, but also potassium bicarbonate, potassium bisulfate, sodiumdihydrogen phosphate, potassium dihydrogen phosphate, disodium hydrogenphosphate, dipotassium hydrogen phosphate, calcium hydrogen phosphate ormagnesium hydrogen phosphate.

[0163] Particularly suitable neutral alkali metal salts are sodiumsulfate and sodium chloride.

[0164] Examples of suitable aliphatic C₈-C₁₈-monocarboxylic acids,aliphatic di- or tricarboxylic acids, aromatic mono- or dicarboxylicacids, it being possible for the abovementioned carboxylic acidsadditionally to contain hydroxyl and amino groups in the molecule, andaliphatic C₃-C₇-monohydroxy carboxylic acids are fatty acids such aslauric acid, myristic acid, palmitic acid and stearic acid, oxalic acid,malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid,suberic acid, maleic acid, fumaric acid, tartaric acid, malic acid,citric acid, benzoic acid, salicylic acid, anthranilic acid, sulfanilicacid, phthalic acid, α- and β-naphthoic acid, naphthalic acid and lacticacid. Of these, palmitic acid, stearic acid, oxalic acid, malonic acid,succinic acid, glutaric acid, adipic acid, pimelic acid, tartaric acid,citric acid and benzoic acid are preferred. Said carboxylic acids mainlyimprove the color stability on storage in detergent powders.

[0165] It is also possible to employ mixtures of several of saidadditives from one of the listed groups or from different groups.

[0166] The invention also relates to a process for preparing thedescribed solid composition, which comprises mixing together 5-98 partsby weight of heterocyclic compounds I and/or oxime esters II with 2-95parts by weight of inert porous carrier materials in a conventional wayand converting this mixture where appropriate by conventional methodsinto a formulated form suitable for the particular application.

[0167] In a preferred embodiment, this preparation process is carriedout in such a way that a solution or a melt of the heterocycliccompounds I and/or of the oxime esters II is mixed with the inert porouscarrier materials by stirring in, spraying on or impregnating, thesolvent, where present, is substantially removed by distillation ordrying and, if necessary, the resulting mixture is converted, whereappropriate after mixing with other auxiliaries, by conventional methodsinto a formulated form suitable for the particular application. Solventssuitable for this purpose are, in particular, conventional organicsolvents such as alcohols, eg. methanol, ethanol or isopropanol,ketones, eg. acetone, carboxylic esters, eg. methyl or ethyl acetate, orunhalogenated or halogenated hydrocarbons, eg. n-hexane, cyclohexane,toluene, xylene or chlorobenzene.

[0168] A typical preparation process of this type entails the inertporous carrier materials being introduced into the solution of thecompounds I or II in an organic solvent and, where appropriate, admixingother auxiliaries, in particular surfactants. The solvent issubsequently removed virtually completely, which is advantageouslycarried out by distillation at low temperature under reduced pressure,especially when a relatively high-boiling solvent has been employed.Then, if necessary, the product, which results in the form of afree-flowing powder, is subjected to conventional methods of compaction,where appropriate size reduction and screening to a size fraction in therange from, for example, 200 μm to 3 mm -depending on the application.

[0169] If necessary, the storage stability of the solid compositionaccording to the invention can be improved by other subsequenttreatments, for example by coating with fats, oils, melts or solutions.

[0170] In place of the introduction and admixing (stirring in) of thecarrier materials, the solution of the compounds I or II can also besprayed onto the carrier materials by conventional techniques.Impregnation processes can also be used. If the mixtures after thespraying or impregnation process are already in powder form, they canalso be agglomerated directly without further drying in a conventionalmixer, it being necessary where appropriate to add other auxiliaries,especially surfactants, for example in molten form or as highlyconcentrated aqueous solution, and this is followed, where appropriate,by the processing to the required size fraction described above.

[0171] The solid composition according to the invention is mainlysuitable as a solid additive for detergents, bleaches and cleaners, inparticular as stable bleach activator component in such compositions.

[0172] It is thus possible to formulate detergents, bleaches andcleaners which contain 0.1-30% by weight, based on the total amount ofthe formulation, of the solid composition according to the invention.The present invention likewise relates to these detergents, bleaches andcleaners. Other conventional components in detergents, bleaches andcleaners are explained in detail below:

[0173] The cold bleach activators I and II described form the bleachsystem together with bleaches, as a rule peroxy compounds, which arelikewise present in the formulation, normally separately. It is moreoverpossible for the pH of the washing or bleaching or cleaning liquors tovary within wide limits, from the weakly acidic region (pH 4) to thehighly alkaline region (pH 13) depending on the application. Thealkaline range from pH 8 to pH 11 is preferred because it isparticularly advantageous for the activation reaction and the stabilityof the peroxy compound formed.

[0174] For this reason, the bleach activators described are alsopreferably used together with a sodium perborate or a sodium carbonateperhydrate, the solutions of which already have pH values in this range.Examples of other suitable peroxy compounds are phosphate perhydratesand urea perhydrate. It may also occasionally be expedient to change thepH of the medium again, especially into the acidic region, by suitableadditives after the activation reaction has taken place.

[0175] The amounts of bleaches (peroxy compounds) employed are generallychosen so that the liquors contain from 10 to 10,000 ppm active oxygen,preferably from 50 to 5,000 ppm active oxygen. The amount of bleachactivator used also depends on the application. From 0.03 to 1.0 mol,preferably 0.1 to 0.5 mol, of activator is used per mole of inorganicperoxy compound, depending on the required degree of activation, butamounts above or below these limits are also possible in special cases.

[0176] Particularly suitable additional bleach activators which can beemployed in combination with the heterocyclic compounds I or the oximeesters II (in the solid composition according to the invention or aspossibly formulated separate component) are:

[0177] polyacylated sugars, eg. pentaacetylglucose;

[0178] acyloxybenzenesulfonic acids and their alkali metal and alkalineearth metal salts, eg. sodium p-isononanoyloxybenzene-sulfonate orsodium p-benzoyloxybenzenesulfonate;

[0179] N,N-diacylated and N,N,N′,N′-tetraacylated amines, eg.N,N,N′,N′-tetraacetylmethylenediamine and -ethylenediamine,N,N-diacetylaniline, N,N-diacetyl-p-toluidine or 1,3-diacylatedhydantoins such as 1,3-diacetyl-5,5-dimethylhydantoin;

[0180] N-alkyl-N-sulfonylcarbonamides, eg. N-methyl-N-mesylacetamide orN-methyl-N-mesylbenzamide;

[0181] N-acylated cyclic hydrazides, acylated triazoles or urazoles, eg.monoacetylated maleic hydrazide;

[0182] O,N,N-trisubstituted hydroxylamines, eg.O-benzoyl-N,N-succinylhydroxylamine, O-acetyl-N,N-succinylhydroxylamineor O,N,N-triacetylhydroxylamine;

[0183] N,N′-diacylsulfamides, eg. N,N′-dimethyl-N,N′-diacetylsulfamideor N,N′-diethyl-N,N′-dipropionylsulfamide;

[0184] triacylcyanurates, eg. triacetylcyanurate ortribenzoyl-cyanurate;

[0185] carboxylic anhydrides, eg. benzoic anhydride, m-chlorobenzoicanhydride or phthalic anhydride;

[0186] 1,3-diacyl-4,5-diacyloxyimidazolines, eg.1,3-diacetyl-4,5-diacetoxyimidazoline;

[0187] tetraacetylglycoluril and tetrapropionylglycoluril;

[0188] diacylated 2,5-diketopiperazines, eg.1,4-diacetyl-2,5-diketopiperazine;

[0189] acylation products of propylenediurea and2,2-dimethyl-propylenediurea, eg. tetraacetylpropylenediurea;

[0190] α-acyloxypolyacylmalonamides, eg.α-acetoxy-N,N′-diacetylmalonamide;

[0191] diacyldioxohexahydro-1,3,5-triazines, eg.1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine;

[0192] benzo-(4H)1,3-oxazin-4-one with alkyl radicals, eg. methyl, oraromatic radicals, eg. phenyl, in position 2.

[0193] For textile laundering, the bleach activators described can becombined with virtually all conventional ingredients of detergentformulations. It is possible in this way to design formulations suitablespecifically for textile treatment at low temperatures, and thosesuitable in several temperature ranges up to the traditional boilingwash range.

[0194] The principal ingredients of such detergent formulations are,besides bleaches (peroxy compounds) and bleach activators, builders andsurfactants. These compositions may also contain other conventionalauxiliaries and additives such as antiredeposition agents, peroxidestabilizers, electrolytes, optical brighteners, enzymes, perfume oils,foam regulators and activating substances if expedient. The componentsof bleach and cleaner formulations are in principle the same.

[0195] Examples of conventional builders are condensed phosphates,alkali metal silicates, alkali metal carbonates, salts of aminocarboxylic acids such as nitrilotriacetic acid, salts of polyphosphonicacids such as hydroxyethanediphosphonic acid, salts of polycarboxylicacids such as citric acid or polyacrylic acid and insoluble sodiumaluminum silicates of the zeolite NaA and NaX types.

[0196] Particularly suitable surfactants are those of the nonionic andsynthetic anionic surfactant types. Examples of nonionic surfactants arethe polyethylene glycol monoalkyl and monophenyl ethers prepared fromlong-chain alcohols or alkylphenols and ethylene oxide, and thelong-chain alkyl glycosides.

[0197] The anionic surfactants are primarily sulfates and sulfonates oflong-chain compounds, for example alkylbenzenesulfonates, fatty acidester sulfonates, alkanesulfonates, olefin sulfonates, fatty alcoholsulfates and sulfates of polyethylene glycol monoethers. It isfurthermore possible to use soaps and salts of long-chainacylcyanamides, and long-chain succinates and sulfosuccinates.

[0198] Typical textile detergents and bleaches of these types haveapproximately the following composition:

[0199] 0.5-30% by weight, preferably 5-25% by weight, of anionic and/ornonionic surfactants,

[0200] 0.5-60% by weight, preferably 5-50% by weight, of builders fromthe group of condensed phosphates, alkali metal silicates, alkali metalcarbonates, sodium aluminum silicates and mixtures thereof,

[0201] 0-20% by weight, preferably 0.5-8% by weight, of builders fromthe group of salts of amino carboxylic acids, salts of polyphosphonicacids, salts of polycarboxylic acids and mixtures thereof,

[0202] 2-35% by weight, preferably 5-30% by weight, of inorganic peroxycompounds,

[0203] 0.1-30% by weight, preferably 0.5-20% by weight, of the solidcomposition according to the invention,

[0204] ad 100% conventional auxiliaries and additives and water.

[0205] The solid composition according to the invention has theadvantage that it has a sufficiently long shelf life, ie. remainsfree-flowing without forming lumps or agglomerates. During this storagetime there are negligible losses of activity, for example in respect ofthe bleaching action. Detergents, bleaches and cleaners which containthe solid composition according to the invention are usually moreeffective than those containing conventional bleach activators such asN,N,N′,N′-tetraacetyl-ethylenediamine (TAED) in the same amounts.

PREPARATION EXAMPLES Example 1

[0206] 10 g of N-(n-octanoyl)-ε-caprolactam were dissolved in 20 g ofacetone, and 10 g of highly disperse silica with an internal surfacearea of about 190 m²/g and an average particle size of about 7 μm(Sipernat®22S from Degussa) were added. After thorough mixing of thesuspension, the solvent was removed by distillation to leave a dry,free-flowing powder which contained the cold bleach activator uniformlydispersed.

Example 2

[0207] 10 g of N-(n-octanoyl)-ε-caprolactam were dissolved in 20 g ofacetone, and 10 g of the same highly disperse silica as in Example 1, 2g of sodium sulfate, 2 g of citric acid and 1 g of corn starch wereadded. After thorough mixing of the suspension, the solvent was removedby distillation to leave a dry, free-flowing powder which contained thecold bleach activator uniformly dispersed.

[0208] Technical Investigations of Use

[0209] Washing tests were carried out with hydrophilic and hydrophobictest soilings using the product from Example 2, and, for comparison,using unformulated N-(n-octanoyl)-ε-caprolactam andN,N,N′,N′-tetraacetylethylenediamine (TAED). It emerged from this thatthe bleach activator formulated according to the invention has adistinctly greater bleaching action, especially with hydrophobicsoilings such as grass on cotton, than the bleach activator TAED whichrepresents the prior art (see Table 1). The test was carried out in alaunder-o-meter, Atlas standard type, using a heavy duty detergent ofthe following composition (% by weight): linear alkylbenzenesulfonate(50% by weight) 0.8 conventional soap 0.4 conventional fatty alcoholsulfate 12.0 C₁₃/C₁₅-Oxo alcohol reacted with 7 mol 4.7 of ethyleneoxide Magnesium silicate 0.8 Sodium bicarbonate 9.0 Sodium percarbonate18.0 Sodium sulfate 3.2 Sodium citrate dihydrate 5.0 Conventional sheetsilicate 14.0 Zeolite A 15.0 Carboxymethylcellulose 0.6 Water Remainderto 100

[0210] The concentration of bleach activator employed in Table 1 or 2was in each case 5% by weight of active substance based on the amount ofdetergent.

[0211] The tests were carried out under the following conditions: Amountof liquor: 250 g Water hardness: 3.0 mmol/l Ca/Mg/HCO₃ molar ratio:4:1:8 Detergent dose: 4.5 g/l Temperature: 22° C./38° C./60° C. Washingtime: 30 min Soiled fabric 1: 2.5 g of bleached cotton (WFK Krefeld)soiled with chlorophyll Soiled fabric 2: 2.5 g of bleached cotton soiledwith red wine Soiled fabric 3: 2.5 g of unbleached cotton cheeseclothRinsing: 3 × 30 sec with tapwater (14° German hardness)

[0212] The tests were evaluated by measurements of the reflectance onthe dried fabrics. The color strength of each of the test soilingsbefore and after the washing were determined by the method described byA. Kud, Seifen, öle, Fette, Wachse 119 (1993) 590-594 from themeasurements of the reflectance at 18 wavelengths in the range from 400to 700 nm at intervals of 20 nm on the individual test fabrics, and theabsolute bleaching action A_(abs) in % was calculated therefrom. Thebleaching action in % is indicated in the following tables. TABLE 1 Testfabric soiled with grass Temperature Bleach activator 22° C. 38° C. 60°C. TAED 27.2 32.0 41.7 Example 2 30.8 37.6 46.2 (formulated)

[0213] TABLE 2 Temperature Bleach activator 22° C. 38° C. 60° C. a)Soiling with chlorophyll Octanoylcaprolactam 31.1 39.5 45.6 Example 230.8 37.6 46.2 (formulated) b) Soiling with red wine Octanoylcaprolactam60.3 64.0 70.6 Example 2 63.8 67.6 73.9 (formulated) c) Unbleachedcotton cheesecloth Octanoylcaprolactam 7.1 14.1 14.2 Example 2 9.1 13.919.6 (formulated)

[0214] The results of measurements from the washing tests in Table 2show that the formulation, represented by the example ofoctanoylcaprolactam, does not necessarily entail a loss of effect.

We claim
 1. A solid composition consisting essentially of 5-98 parts by5 weight of heterocyclic compounds of the general formula I R¹—X—L¹  (I) where L¹ is (a) a cyclic carbamate residue of the formula

(b) a lactonoxy residue of the formula

or (c) a lactam residue of the formula

where Z¹ to Z³ are 1,2-, 1,3-, 1,4- or 1,5-alkylene groups which have 2to 20 carbon atoms, and which can additionally be functionalized by oneto three hydroxyl groups, C₁-C₄-alkoxy groups, amino groups, C₁-C₄-alkylamino groups, di-C₁-C₄-alkylamino groups, chlorine atoms, bromine atoms,nitro groups, cyano groups, carboxyl groups, sulfo groups,carboxy-C₁-C₄-alkyl groups, carboxamide groups or phenyl, tolyl orbenzyl radicals, it likewise being possible for aromatic nuclei in turnto be substituted by said radicals, or interrupted by one or twonon-adjacent oxygen atoms, amino groups, C₁-C₄-alkylamino groups orcarbonyl groups, and T is hydrogen or C₁-C₄-alkyl, X is anoxygen-containing group of the formula

where Y is hydrogen, ammonium which can be unsubstituted or substitutedby organic radicals, or C₁-C₄-alkyl, and A is a chemical bond or aC₁-C₁₈-alkylene group, a C₂-C₁₆-alkenylene group, a C₅-C₃₂-cycloalkylenegroup, a C₇-C₃₀-aralkylene group, a C₆-C₁₈-arylene group or aC₃-C₁₈-hetarylene group, it additionally being possible for aliphaticstructural units to be functionalized by one to five hydroxyl groups,C₁-C₄-alkoxy groups, amino groups, C₁-C₄-alkylamino groups,di-C₁-C₄-alkylamino groups, chlorine atoms, bromine atoms, nitro groups,cyano groups, carboxyl groups, sulfo groups, carboxy-C₁-C₄-alkyl groups,carboxamide groups or phenyl, tolyl or benzyl radicals, it likewisebeing possible for aromatic, cycloaliphatic and heteroaromaticstructural units to be substituted by said radicals, or interrupted byone to eight non-adjacent oxygen atoms, amino groups, C₁-C₄-alkylaminogroups or carbonyl groups, and R¹ has the following meaning:C₁-C₃₀-alkyl, C₂-C₃₀-alkenyl, C₅-ClB-cycloalkyl, C₇-C₁₈-aralkyl,C₆-C₁₈-aryl or C₃-C₁₈-hetaryl, it being additionally possible foraliphatic radicals to be functionalized by one to five hydroxyl groups,C₁-C₄-alkoxy groups, amino groups, C₁-C₄-alkylamino groups,di-C₁-C₄-alkylamino groups, chlorine atoms, bromine atoms, nitro groups,cyano groups, carboxyl groups, sulfo groups, carboxy-C₁-C₄-alkyl groups,carboxamide groups or phenyl, tolyl or benzyl radicals, it likewisebeing possible for aromatic, cycloaliphatic and heteroaromaticstructural units to be substituted by said radicals, or interrupted byone to eight non-adjacent oxygen atoms, amino groups, C₁-C₄-alkylaminogroups or carbonyl groups, or a heterocyclic radical L¹, and/or oximeesters of the general formula II

where L² is an oxime moiety of the formula

where R² and R³ are hydrogen, C₁-C₃₀-alkyl, C₂-C₃₀-alkenyl,C₅-C₁₈-cycloalkyl, C₇-C₁₈-aralkyl, C₆-C₁₈-aryl or C₃-C₁₈-hetaryl, itbeing additionally possible for aliphatic radicals to be functionalizedby one to five hydroxyl groups, C₁-C₄-alkoxy groups, amino groups,C₁-C₄-alkylamino groups, di-C₁-C₄-alkyl-amino groups, chlorine atoms,bromine atoms, nitro groups, cyano groups, carboxyl groups, sulfogroups, carboxy-C₁-C₄-alkyl groups, carboxamide groups or phenyl, tolylor benzyl radicals, it likewise being possible for aromatic,cycloaliphatic and heteroaromatic structural units to be substituted bysaid radicals, or interrupted by one to eight non-adjacent oxygen atoms,amino groups, C₁-C₄-alkylamino groups or carbonyl groups, and Z⁴ is1,3-, 1,4-, 1,5-, 1,6-, 1,7- or 1,8-alkylene groups which have 3 to 30carbon atoms and which can additionally be functionalized by one to fivehydroxyl groups, C₁-C₄-alkylamino groups, di-C₁-C₄-alkylamino groups,chlorine atoms, bromine atoms, nitro groups, cyano groups, carboxylgroups, sulfo groups, carboxy-C₁-C₄-alkyl groups, carboxamide groups orphenyl, tolyl or benzyl radicals, it likewise being possible foraromatic nuclei in turn to be substituted by said radicals, orinterrupted by one or two non-adjacent oxygen atoms, amino groups,C₁-C₄-alkylamino groups or carbonyl groups, L³ is the radical R¹, asecond oxime moiety L² or (a) a carboxylic ester residue of the formula

(b) a carboxamide residue of the formula

(c) a phenolate residue of the formula

(d) a vinyloxy-radical of the formula —O—CR²═CHR³ (e) a sulfonamideresidue of the formula

(f) an imidazole residue of the formula

(g) an amidolactam residue of the formula

(h) a cyclic carbamate residue of the formula

(j) a lactonoxy residue of the formula

or (k) a lactam residue of the formula

where R¹, R², R³, T, Z¹ to Z³ and A have the abovementioned meanings, R⁴is hydrogen, a carboxyl group, a sulfo group, a phosphono group or thealkali metal or ammonium salt thereof, and m is the number 0 or 1, and2-95 parts by weight of inert porous carrier materials with an internalsurface area of from 10 to 500 m²/g.
 2. A solid composition as claimedin claim 1, wherein the inert porous carrier materials have an averageparticle size of from 3 nm to 2 mm.
 3. A solid composition as claimed inclaim 1 or 2, wherein silica gels, silicas, aluminum oxide, kaolinsand/or aluminum silicates are employed as inert porous carriermaterials.
 4. A solid composition as claimed in any of claims 1 to 3,wherein the oxygen-containing group X in the heterocyclic compounds I is


5. A solid composition as claimed in any of claims 1 to 4, wherein theradical R¹ in the heterocyclic compounds I is C₆-C₁₈-alkyl,C₆-C₁₈-alkenyl, C₇-C₁₂-aralkyl, phenyl or alkyl-substituted phenyl witha total of up to 14 carbon atoms or a second heterocyclic radical L¹which has the same structure as the first heterocyclic radical L¹.
 6. Asolid composition as claimed in any of claims 1 to 3, wherein theradical L² in the oxime esters II is an oxime moiety of the formula

where R⁵ and R⁶ are hydrogen, C₁-C₄-alkyl, phenyl or benzyl, and Z⁵ is1,4-butylene, 1,5-pentylene or 1,6-hexylene.
 7. A solid composition asclaimed in any of claims 1 to 3 or 6, wherein the radical L³ in theoxime esters II is a second oxime moiety L² or a C₁-C₁₈-alkyl radical, aC₂-C₁₈-alkenyl radical, a C₇-C₁₂-aralkyl radical or phenyl oralkyl-substituted phenyl with a total of up to 14 carbon atoms.
 8. Aprocess for preparing a solid composition as claimed in any of claims 1to 7, which comprises mixing together 5-98 parts by weight ofheterocyclic compounds I and/or oxime esters II with 2-95 parts byweight of inert porous carrier materials in a conventional way andconverting this mixture where appropriate by conventional methods into aformulated form suitable for the particular application.
 9. A processfor preparing a solid composition as claimed in claim 8, wherein asolution or a melt of the heterocyclic compounds I and/or of the oximeesters II is mixed with the inert porous carrier materials by stirringin, spraying on or impregnating, the solvent, where present, issubstantially removed by distillation or drying and, if necessary, theresulting mixture is converted, where appropriate after mixing withother auxiliaries, by conventional methods into a formulated formsuitable for the particular application.
 10. A detergent, bleach orcleaner comprising 0.1-30% by weight, based on the total amount of theformulation, of the solid composition as claimed in any of claims 1 to7.
 11. The use of a solid composition as claimed in any of claims 1 to 7as stable bleach activator component in detergents, bleaches andcleaners. Solid composition consisting of heterocyclic compounds and/oroxime esters and inert porous carrier materials and the use thereof asstable bleach activator component in detergents, bleaches and cleanersAbstract A solid composition consisting essentially of 5-98 parts byweight of heterocyclic compounds I R¹—X—L¹   (I) where L¹ is groups witha cyclic carbamate, a lactonoxy or a lactam structure, X is a carbonyl,a doubled carbonyl or a heterocarbonyl group, and R¹ is an organicradical or a second moiety L¹, and/or oxime esters II

where L² is an oxime moiety

where R², R³ and Z⁴ are organic radicals or linkers, L³ is the radicalR¹, a second oxime moiety L² or a carboxylic ester residue, carboxamideresidue, phenolate residue, vinyloxy radical, sulfonamide residue,imidazole residue, amidolactam residue, cyclic carbamate residue,lactonoxy residue or lactam residue, and m is 0 or 1, and 2-95 parts byweight of inert porous carrier materials with an internal surface areaof from 10 to 500 m²/g. The solid composition described is suitable asstable bleach activator component in detergents, bleaches and cleaners.